Browse > Article
http://dx.doi.org/10.5012/jkcs.2006.50.4.281

Theoretical Studies on the Structure and Aromaticity of 1H-Indene and Mono-sila-1H-Indene  

Ghiasi, Reza (Islamic Azad University(IRAN))
Monnajemi, Majid (Islamic Azad University(IRAN))
Publication Information
Journal of the Korean Chemical Society / v.50, no.4, 2006 , pp. 281-290 More about this Journal
Abstract
The electronic structure and properties of the 1H-indene and mono-sila-1H-indene series have been investigated using basis set of 6-31G(d, p) and hybrid density functional theory. Basic measures of aromatic character derived from structure, molecular orbitals, a variety of magnetic criteria (magnetic isotropic and anisotropic susceptibilities) are considered. Energetic criteria suggest that In(Si7) enjoy conspicuous stabilization. However, by magnetic susceptibility isotropic this system are among the least aromatic of the family: Within their isomer series, In(Si4) is the most aromatic using this criteria. Natural bond orbital (NBO) analysis method was performed for the investigation of the relative stability and the nature of the 8-9 bonds in 1H-indene and mono-sila-1H-indene compounds. The results explained that how the p character of natural atomic hybrid orbital on X8 and X9 (central bond) is increased by the substitution of the C8 and C9 by Si. Actually, the results suggested that in these compounds, the X8-X9 bond lengths are closely controlled by the p character of these hybrid orbitals and also by the nature of C-Si bonds. The magnitude of the molecular stabilization energy associated to delocalization from X8-X9 and to * X8-X9 bond orbital were also quantitatively determined. Molecular orbital (MO) analysis further reveal that all structure has three delocalized MOs and two delocalized MOs and therefore exhibit the aromaticity.
Keywords
1H-Indene; Sila-1H-Indene; Aromaticity; magnetic properties; Natural bond orbital (NBO)
Citations & Related Records

Times Cited By SCOPUS : 1
연도 인용수 순위
1 Katritzky, A. R.; Rees, C. W.; Scrivem, E. F. (Editors-in-Chief) Comprehensive Heterocyclic Chemistry, A review of the Literature 1982–1995. The Structure, Reactions, Synthesis and Uses of Heterocyclic Compounds, Pergamon Press, UK, 1996
2 Krygowski, T. M.; Cvranski, M. K; Czarnocki Z.; Hafelinger, G.; Katrizky., Tetrahedron, 2000, 56, 1783   DOI   ScienceOn
3 Kuznetsov, A. E.; Boldyrev, A. I.; Li, X.; Wang, L. S. J. Am. Chem. Soc. 2001, 123, 8825   DOI   ScienceOn
4 Zilberg, S.; Kendler, S.; Haas, Y. J. Phys. Chem. 1996, 100, 10869   DOI   ScienceOn
5 Southern, J.F.; Scha¨fer, L.; Brendhaugen, K.; Seip, H. M. J. Chem. Phys. 1971, 55, 2418   DOI
6 Barton, D.; Ollis, W.D. Comprehensive Organic Chemistry: The Synthesis and Reactions of Organic Compounds, Pergamon Press, New York, 1979
7 Schleyer, P. v. R.; Jiao, H.; Pure Appl. Chem. 1996, 68, 209   DOI
8 Cheeseman, J. R.; Frisch, M. J.; Trucks G. W.; Keith, T. A.; J. Chem. Phys. 1996, 104, 5497   DOI
9 Keith, T. A.; Bader, R. F. Chem. Phys. Lett. 1993, 210, 223   DOI   ScienceOn
10 Li, Y. S.; Jalilian, M. R.; Durig, J. R. J. Mol. Struct. 1979, 51, 171   DOI   ScienceOn
11 Pearson, R. G.; J. Org. Chem. 1989, 54, 1423   DOI
12 Z. Zhou, R. G. Parr, J. Am. Chem. Soc. 1989, 111, 7371   DOI
13 Minsky, A.; Meyer, A. Y.; Rabinovitz, M.; Tetrahedron, 1985, 41, 785   DOI   ScienceOn
14 Pearson, R. G.; Inorg. Chem. 1988, 27, 734   DOI
15 Becke, A. D.; J. Chem. Phys. 1993, 98, 5648   DOI   ScienceOn
16 Schleyer, P. v. R.; Maerker, C.; Dransfekd, A.; Jiao, H.; Homm, N. v. E. J. Am. Chem. Soc. 1996, 118, 6317   DOI   ScienceOn
17 Goldfuss. B.; Schleyer. P. v. R.; Hampel. F. Organometallics, 1996, 15, 1998
18 Carpenter, J. E.; Weinhold, F. J. Mol. Struct. (THEOCHEM). 1988, 169, 41   DOI   ScienceOn
19 Lee, C.; Yang, W.; Parr, R. G.; Phys. Rev. B. 1988, 37, 785   DOI   ScienceOn
20 Klots, T. D. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 1995, 51, 2307   DOI   ScienceOn
21 Collins, J. B. Schleyer, P. v. R. Inorg. Chem. 1977, 16, 152   DOI
22 Jemmis, E. D.; Alexandratos, S.; Schleyer, P. v. R. Streitwieser, A.; Schaefer, H. F. J. Am. Chem. Soc. 1978, 100, 5695   DOI
23 Krogh-Jespersen, K.; Chandrasekhar, J.; Schleyer, P. v. R. J. Org. Chem. 1980, 45, 1608   DOI
24 Minkin, V. J; Glukhovesev, M. N.; Simkin, B. Y. Aromaticity and Antiaromaticity: Electronic and Structural Aspects; Wiley: New York, 1984
25 Li, X.; Kuznetsov, A. E.; Zhang, H. F.; Boldyrev, A. I.; Wang, L. S. Science, 2001, 291, 859   DOI   ScienceOn
26 A. E.Kuznetsov, J. D. Corbett, L. S. Wang, A. I. Boldyrev, Angew. Chem., Int. Ed. 2001, 40, 3369   DOI   ScienceOn
27 Patai, S.; Rappoport, Z.; Eds, The Chemistry of Organic Silicon Compounds; Wiley: New York, 1989; p 1015
28 Schleyer, P. v. R.; Jiao, H. Pure Appl. Chem. 1996, 68, 209   DOI
29 Andres L. S.; Borin, A. C. Chemical Physics. 2000, 26, 267   DOI   ScienceOn
30 Reed, A. E.; Curtiss, L. A.; Weinhold, F.; Chem. Rev. 1988, 88, 899   DOI
31 Fowler, P. W.; Havenith, R. W. A.; Steiner, E. Chem. Phys. Lett. 2001, 342, 85   DOI   ScienceOn
32 Fowler, P. W.; Havenith, R. W. A.; Steiner, E. Chem. Phys. Lett. 2001, 359, 530
33 Katrizky, A. R.; Barczynski, P.; Musumarra, G.; Pisano, D.; Szafran, M. J. Am. Chem. Soc. 1989, 111, 7   DOI
34 Jug, K.;. Koster, A. M. J. Phys. Org. Chem. 1991, 4, 163   DOI
35 Schleyer, P. v. R.; Freeman, P. K.; Jiao, H.; Goldfuss, B., Angew.Chem., Int. Ed. Engl. 1995, 34, 337   DOI   ScienceOn
36 Bird, C. W. Tetrahedron, 1996, 52, 9945   DOI   ScienceOn
37 Garrat. P. J. Aromaticity; Willey: New York. 1986
38 Li, X. W.; Pennington, W. T; Robinson, G. H.; J. Am. Chem. Soc. 1995, 117, 7578   DOI   ScienceOn
39 Gaussian 98, Revision A.7, Frisch, M. J.; Trucks, G. W; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, J. R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. E.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; and Pople, J. A.; Gaussian, Inc., Pittsburgh PA, (1998)
40 Li, W. Q; Tian, W. Q.; Feng, J. K; Liu, Z. Z.; Ren, A M.; Zhang, G. J. Phys. Chem. A, 2005, 109, 8391   DOI   ScienceOn
41 Robinson, G. H. Acc. Chem. Res. 1999, 32, 773   DOI   ScienceOn
42 Ghiasi, R. J. Mol. struc (THEOCHEM). 2005, 718, 225   DOI   ScienceOn
43 Ghiasi, R. J. Organome. Chemistry. 2005, 690, 4761   DOI   ScienceOn
44 Zhou, Z.; Parr, R. G.; Tetrahedron Lett. 1988, 29, 4843   DOI   ScienceOn
45 A. A. El-Azhary, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 1999, 55, 2437   DOI   ScienceOn
46 Li, X. W.; Xie, Y.; Schreiner, P. R.; Gripper, K. D.; Crittendon, R. C.; Campana, C. F.; Schaefer, H. F.; Robinson, G. H.; Organometallics. 1996, 15, 3798   DOI   ScienceOn
47 Pearson, R. G.; J.Am. Chem. Soc. 1988, 110, 2092   DOI